Carbamaldoximes

ABSTRACT

NOVEL CARBAMALDOXIMES OF THE FORMULA   X-C(-Y)=N-O-CO-NH-C(-CL)=C(-CL)2   WHERE Y IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, CHLORINE AND BROMINE AND X IS SELECTED FROM THE GROUP CONSISTING OF PHENYL OPTIONALLY SUBSTITUTED WITH AT LEAST ONE MEMBER OF THE GROUP CONSISTING OF HALOGEN CYANO-NO2, ALKYLL OF 1 TO 6 CARBON ATOMS AND ALKOXY OF 1 TO 6 CARBON ATOMS AND NITROFURYL HAVING FUNGICIDAL ACTIVITY.

United States Patent 3,836,582 CARBAMALDOXIMES Jacques Perronnet and Pierre Girault, Paris, France, assiguors to Roussel-UCLAF, Paris, France No Drawing. Filed Oct. 23, 1973, Ser. No. 408,744 Claims priority, appli ggfigii France, Nov. 6, 1972, 3 4

Int. Cl. C07c 131/00 US. Cl. 260-566 AC 2 Claims ABSTRACT OF THE DISCLOSURE Novel carbamaldoximes of the formula 0 XC=NO lNHC=C C12 wherein Y is selected from the group consisting of hydrogen, chlorine and bromine and X is selected from the group consisting of phenyl optionally substituted with at least one member of the group consisting of halogen, cyano, -NO alkyl of l to 6 carbon atoms and alkoxy of 1 to 6 carbon atoms and nitrofuryl having fungicidal activity.

STATE OF THE ART US. Pat. No. 3,742,036 describes aldoximes of the formula Cl R2 wherein R and R are lower alkyl and R is hydrogen or lower alkyl having biocidal, fungicidal or bactericidal properties but these are chemically distinct from the compounds of formula I.

OBJECTS OF THE INVENTION It is an object of the invention to provide the novel carbamaldoximes of formula I and a process for their preparation.

It is another object of the invention to provide novel fungicidal compositions and to provide a novel method of combatting fungi.

These and other objects and advantages of the invention will become obvious from the following detailed description.

THE INVENTION The novel carbamaldoximes of the invention have the formula X-o=N oH Y I! wherein X and Y have the above definition. The reaction ice is preferably effected in the presence of an organic solvent such as toluene or tetrahydrofuran and a tertiary base such as triethylamine or pyridine.

The aldoximes of formula II can be prepared by known methods such as condensing hydroxylamine with the appropriate aldehyde.

The novel fungicidal compositions of the invention are comprised of an effective amount of at least one compound of formula I and a carrier. The compositions can also optionally contain one or more other pesticides or other products influencing the growth of plants.

The compositions may be in the form of powders, granules, suspensions, emulsions or solutions, containing besides the active ingredients, cationic, non-ionic or anionic surface active agents; inert powders such as talc, clays, silicates, Kieselguhr, etc.; or a vehicle such as water, alcohol, hydrocarbons or other organic solvents, mineral, vegetable or animal oils, etc.

The fungicidal powders used for foliar spraying preferably contain 25 to 95% by weight of the compounds of formula I and the fungicidal compositions used as foliar powders preferably contain 2.5 to 99% by weight of the compounds of formula I.

An example of a composition for a foliar spray comprises 25% by weight of O-[N-trichlorovinylcarbamoyl]- a,p-dichlorobenzaldoxime, 15% by weight of Ekapersol S (condensation product of sodium naphthalene sulfonate), 0.5% by weight of Brecolane NVA (sodium alkyl naphthalene sulfonate), 34.5% by weight of Zeosil 39 (precipitated synthetic hydrated silica) and 25% by weight of Vercoryl S (colloidal Kaolin).

For the protection of paints against fungi, the active compound of formula I may be incorporated during grinding of the pigments. The concentration of the products of formula I is preferably 0.05 to 5% by weight of the paint. For example, 1% by weight of O-[N-trichlorovinylcarbamoyl] a-p-dichlorobenzaldoxime is added to the pigments during grinding to obtain a paint protected against fungi.

The novel method of the invention for killing fungi comprises contacting fungi with a fungicidal amount of at least one compound of formula I. The method is useful in agriculture and in protecting paints.

In the following examples there are described several preferred embodiments to illustrate the invention. However, it should be understood that the invention is not intended to be limited to the specific embodiments.

EXAMPLE I O- [N-trichlorovinylcarbamoyl] -a,p-dichlorobenzaldoxime 19 g. of u,p-dichlorobenzaldoxime [Farley, Proc. N. Dakota Acad. Sci., Col. 13 (1959), p. 61] and 20 g. of trichlorovinyl isocyanate, Pat. No. 3,468,923) were added to ml. of toluene and the mixture was stirred for 30 minutes at C. The toluene was removed by distillation under reduced pressure and the residue was added to petroleum ether (boiling point 65-7S C.) containing 10% isopropyl ether. The crystals formed were recovered by vacuum filtration and dried to obtain 27.2 g. of O [N trichlorovinylcarbamoyl] a,p-dichlorobenzaldoxime melting at 92 C.

Analysis: C H Cl N O .Calculated (percent): C, 33.14; H, 1.39; Cl, 48.92; N, 7.73. Found (percent): C, 33.3; H, 1.8; Cl, 48.5, N, 7.5.

EXAMPLE II O-[N-trichlorovinylcarbamoly]-5-nitro-furfuraldoxime 25 g. of 5-nitro-furfuraldoxime [Rev. Chim. Acad. Rep. populaire de Roumainie, I No. 1 (1956), pp. 164] were added to 250 ml. of tetrahydrofuran and 3 4 after cooling to 5 C., 1 ml. of triethylamine was added placed in dishes containing a gelose nutritive medium free thereto. Slowly, 36 g. of raw trichlorovinyl isocyanate from assimilable carbon and comprised of 3 g. of am (78% purity) were added and the mixture was stirred for monium nitrate, 0.5 g. of magnesium sulfate, 0.25 g. of 6 hours. The precipitate formed was recovered by potassium chloride, 1 g. of monopotassium phosphate,

vacuum filtration and was washed with petroleum ether 5 15 g. of agaragar and 1000 g. of demineralised water. (boiling point 6575 C.), methanol and isopropyl Before addition of agar-agar, the pH was adjusted to ether and dried to obtain 23.7 g. of O-[N-trichlorovinyl- 6-7. Each dish contained 2 test pieces and 4 tests were carbamoyl]-5-nitrofurfuraldoxime melting at 158 C. run for each concentration.

Analysis: C H Cl N O .Calculated (percent): C, The test pieces were contaminated by placing on each 29.25; H, 1.22; N, 12.79; Cl, 32.38. Found (percent): 10 test piece drops of a fungi spore suspension of Peni- C, 29.3; H, 1.1; N, 12.5, C1, 32.3. cillium luteum, Myrothecium verrucaria, Cladosporium EXAMPLE HI herborum, Stachybotr ys atra, Pae cylomyces varioti, Ifullularza pullulans, Irzchoderma lzgnorum, Chaetomzum The Protective activity of -l y a globosum and Aspergillus niger. The samples were stored bflmoyl]mP-dichlofobenlaldOXime for Paints against in a tropical room at C. and relative humidity fungi comprised incorporating 10 ml. of n a one sol for three months. The attack before washing and after tion of the test compound into g. of paint (oil or washing (developments above all samples, developments water base paint) to obtain a concentration of 2, 1, 0.5 by placement of drops; stains "at the placement of the or 0.25% by weight of the active compound. Layers of drops, no attack) was noted. The washing was for the paint were prepared by spreading the paint thus treated 20 purpose of eliminating the stains caused by superificial on polyethylene sheets while the control layers were undevelopment of mould, which do not correspond to an treated. After drying at 24 to 48 hours, the paint layers effective attack of the paint. The results of the following were removed from the polyethylene and were cut into Tables show that the test compound has a good activity 5 x 2 cm. pieces. The said test pieces of paint were for protecting paints against the various moulds tested.

Stachybotrys atra Water base paint Oil-base paint Before washing After washing Before washing After washing Concentration, percent MA 2 1 0.5 0.25 2 1 0.5 0.25 2 1 0.5 0.25 2 1 0.5 0.25

Development over all the test piece Development at the placement of the drops Stains at the placement of the drops Total protection Paecylomyces varioti Water base paint Oil-base paint Before washing After washing Before washing After washing Concentration, percent MA 2 1 0. 5 0. 25 2 1 0.5 O. 25 2 1 0. 5 0. 25 2 1 0. 5 0. 25

Development over all the test piece Development at the placement of the drops 1 Stains at the placement of the drops Total protection Pullularz'a pullulrms Water base paint Oil-base paint Before washing After washing Before washing After washing Concentration, percent MA 2 1 0. 5 0. 25 2 1 0. 5 0. 25 2 1 0.5 0. 25 2 l 0. 5 0. 25

Development over all the test piece Development at the placement of the drops Stains at the placement of the drops- Total protection Trichodcrma Zignorium Water base paint Oil-base paint Before washing After washing Before washing After washing Concentration, percent MA 2 1 0.5 O. 25 2 1 0.5 0.25 2 l 0.5 0. 25 2 1 0. 5 0. 25

Development over all the test piece Development at the placement of the drops Stains at the placement of the drops- Total protection Ghactomium globosmn Water base paint Oil-base paint Before washing After washing Before washing After washing Concentration, percent MA 2 1 0. 5 0. 25 2 1 0. 5 0. 25 2 1 0. 5 0. 25 2 l 0. 6 0. 25

Development over all the test piece Development at; the placement of the drops Stains at the placement of the drops Total protection ltspm'g'illus m'ger Water base paint Oil-base paint Before washing After washing Before washing After washing Concentration, percent MA 2 1 0. 5 0.25 2 1 0.5 0. 25 2 1 0.5 0.25 2 l 0.5 0. 25

iiifififiifit itt titifliifitii fteerase: '11:: '1 "5 Stains at the placement of the drops e Total protection Penicillium lulcum Water base paint Oil-base paint Before washing After washing Before washing After washing Concentration, percent MA 2 1 0. 5 0.25 2 1 0.5 0.25 2 1 0.5 0.25 2 1 0.5 0.25

Development over all the test piece Development at the placement of the drops Stains at the placement of the drops Total protection Myrothecium verrucarz'a Water base paint Oil-base paint Before washing After washing Before washing After washing Concentration, percent MA 2 1 0. 5 25 2 l 0. 0. 2 1 0. 5 0. 25 2 1 0. 5 0. 25

Development over all the test piece Development at the placement of the drops Stains at the placement of the drops Total protection Oladosporium herbarum Water base paint Oil-base paint Before washing After washing Before washing After washing Concentration, percent MA 2 1 0- 5 0. 2 2 1 0. 5 0. 25 2 1 0.5 0.25 2 1 0. 5 0. 25

Development over all the test piece. Development at the placement of the drops- Stains at the placement of the drops Total protection Various modifications of the products and methods of cyano, -NO alkyl of 1 to 6 carbon atoms and alkoxy the invention may be made without departing from the of 1 to 6 carbon atonm spirit or scope thereof and it should be understood that 2 A compound of l i 1 hi h i Q. N-t i h1 the invention is to be limited only as defined in the apvinylcarbamoyl] uPdichlorobenZaldoxime pended claims.

y A c riiiipound of the formula References Cited UNITED STATES PATENTS 0 3,223,733 12/1965 Heiss et a1 260-566 AC F I1 f 3,553,264 1/1971 Addor 260-566 AC Y Cl BERNARD HELFIN, Primary Examiner wherein Y is selected from the group consisting of hy- SCHWARTZ Asslstant Exammer drogen, chlorine and bromine and X is selected from the U 5 Cl X R group consisting of phenyl optionally substituted with at least one member of the group consisting of halogen, 260-347], 465 E; 424-304, 327 

